JPS63233941A - Polyacetal, manufacture and use - Google Patents

Abstract

Polyacetals obtainable by reaction of (a) a dialdehyde of the formula OHC-An-CHO where A=C1-C4-alkylene or <IMAGE> and n is 0 or 1, is reacted with (b) a polycarboxylic acid of 5 to 7 carbon atoms which contains not less than 3 OH groups, in a molar ratio (a):(b) of 1:0.25 to 4 in an aqueous medium in the presence of an acid catalyst, are used as additives in washing agents and as complexing agents for heavy metal ions.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyacetals obtained from dialdehydes and polyol carboxylic acids, and their uses.

Legislative regulations in many countries recommend strongly reducing the phosphate content in detergents or making detergents phosphate-incompatible. Reducing the content of phosphates in detergents
Naturally, its cleaning action deteriorates. Therefore, there is a need for additives that can replace all or part of phosphates in detergents.

The object of the invention was to develop new substances which can be used as additives to reduce or eliminate phosphates in detergents and which can improve the cleaning action of detergents.

The present invention solves this problem by converting a dialdehyde (a) represented by the following formula: Polyol carboxylic acid (b) having an OH group, and (a
) : A polyacetal obtained by reacting (b) in a molar ratio of 1:0.25 to 4 in an aqueous medium in the presence of an acidic catalyst.

This polyacetal is a polyacetal containing a dialdehyde (a) of the following formula %, where n is 0 or 1, having 5 to 7 carbon atoms and few (all 3 OH groups). Carboxylic acid (b) and (a
) : (b) in a molar ratio of 1:0.25 to 4 in an aqueous medium in the presence of an acidic catalyst at a temperature below 140°C and by removing water from the reaction mixture during or after the reaction. Manufactured.

Components (a) and (1)) are in a molar ratio of 1:0.5 to 60
Preferably, the reaction is carried out at a temperature of -110°C.

Examples of suitable dialdehydes (a) are glyoxal, malondialdehyde, succinic dialdehyde, glutardialdehyde, adipine dialdehyde or terephthalic dialdehyde. Mixtures of these dialdehydes can be used as well.

Other dialdehyde derivatives which release the basic dialdehyde under the synthetic conditions, such as open-chain acetals such as glyoxal tetramethyl acetal, glyoxal tetraethylacetal or glutardialdehyde-tetramethyl acetal, half-acetals such as 2,3-dihydroxy-1,4 -Dioxane or disulfates of dialdehydes such as glyoxal disulfate can also be used. Glyoxal, glutardialdehyde or terephthaldialdehyde, or a mixture of glyoxal and glutardialdehyde, a mixture of glyoxal and terephthaldialdehyde, a mixture of glutardialdehyde and terephthaldialdehyde, or a combination of glyoxal, glutardialdehyde and terephthaldialdehyde. Preferably, the mixture is used in the reaction as an aqueous solution.

The polyoxycarboxylic acid (b) is derived from a mono- or dicarboxylic acid having 5 to 7 carbon atoms and at least 6 OH groups in the molecule, and for example, the following sugar carboxylic acids are used.

Ribbonic acid, lyxonic acid, mannonic acid, altronic acid, allonic acid, curconic acid, 2-ketocurconic acid, 2,5-diketogluconic acid, gulonic acid, idonic acid, kydyuronic acid, gulonic acid, galactonic acid, mannosaccharic acid, glucal acids, galafthalic acid, allomucic acid, glucoheptonic acid, talomucic acid, idosugar acid or its lactones or dilactones. Gluconic acid and/or glucoheptonic acid is preferably used as component (b).

Components (a) and (1)) are reacted in a molar ratio of 1:0.25 to 4, preferably 1:0.5 to 2. In order for the reaction to proceed well, it is necessary to carry out the reaction in the presence of an acidic catalyst. For this purpose, non-volatile strong acids with a pKa value of 1 or less are used. Examples are p-dololsulfonic acid, sulfuric acid, amidosulfonic acid, methanesulfonic acid and hibenzolesulfonic acid.

As the acidic catalyst, acidic groups such as 803H group or COO
Ion exchangers with H groups are also suitable.

The catalyst has components (a) and (b) used in the reaction,
It is used in an amount of 0.5 to 10% by weight, preferably 1 to 5% by weight. The reaction takes place within a wide temperature range, e.g.
It can be carried out preferably at 60 to 110°C. If the temperature is above the boiling temperature of the respective reaction mixture used, the reaction is carried out under pressure, for example in an autoclave.

The reaction is usually carried out at normal pressure, but it is also possible to carry out the reaction under reduced pressure.

The reaction between (a) and (1)) is carried out in an aqueous medium, with (a) and fb
) concentration in total is 20-80% by weight, preferably 60-7
It is carried out at 0% by weight. The reaction can also be carried out in the presence of an inert organic solvent in which the polyacetal is insoluble. The polyacetal is then obtained in finely divided form. As inert organic solvents, both aliphatic and aromatic hydrocarbons can be used, examples being pentane, hexane, cyclohexane, hegetane, n-octane, inoctane, nonane, decane,
Methylcyclohexane, penzole, doluol, 0-
They are quidylol, p-xyllol, m-quidilol, ethylpenzole and hinglobilbenzole. In addition, chlorinated hydrocarbons such as chloroform, carbon tetrachloride,
Methylene chloride and tetrachloroethane can also be used, as can inert organic solvents. The weight ratio between the amount of inert organic solvent and the amount of water used is about 10:1 to 1:10, preferably 5:1.
The ratio is 1 to 1:2. Water and (
The water formed in the reaction of a) and (b) is removed from the reaction mixture to produce the polyacetal. Polycarboxylic acid, ie, moles of water, is produced and removed from the reaction mixture.

The reaction of components (a) and (b) can further be carried out in the presence of a water-in-oil emulsifier. HLB of water-in-oil emulsifier
Values range between 2 and about 8. For the definition of HLB value,
Journal e of Q Society op Cosmetic
Reference is made to Chemistry, Vol. 5, p. 249 (1954). Examples of water-in-oil emulsifiers having the above HLB values include oleic acid triethanolamine ester, oleic acid jetanolamide, sorbitan monooleate, sorbitan tristearate, mannitol monooleate, glycerin monooleate, and glycerin dioleate. It is oleate.

With respect to the amount of water present during polyacetal production, 0 to
60% by weight, preferably 1 to 10% by weight, of water-in-oil emulsifier is used. In addition to the water-in-oil emulsifiers mentioned above, emulsifiers with an HLB value greater than 8 can also be used, examples of which are as follows. Polyethoxylated alkylphenols, their sulfuric esters, C8o-020-alkylsulfonates, alkali metal, ammonium or amine soaps, sulfated or sulfonated oils, alkali metal salts of alkylarylsulfonic acids, salts of long-chain amines, e.g. Oleylamine acetate, c, ~c2□ - ethylene oxide adducts to fatty alcohols or to fatty acid amides (the amides being derived from fatty acids having 10 to 18 carbon atoms). Ethylene oxide adducts to alkylphenols, fatty alcohols or fatty acid amides have 5 to 40 ethylene oxide units in the molecule.

The reaction between dialdehyde and polyol carboxylic acid is carried out continuously or discontinuously. For example, a portion of an aqueous solution of dialdehyde and polycarboxylic acid is charged to a reactor, where 2
A complete reaction is first carried out at a temperature of 5 to 140°C, and then the remainder is added intermittently or continuously to form a polyacetal. The catalyst may, for example, be charged first or may be fed to the reactor together with one or both reaction components. Water is distilled off from the reactor during or after polyacetal production.

However, if the water-in-oil emulsion is charged to the reactor and the components (
It is also possible for a) and (b) to be introduced into this emulsion separately or in a mixture. The catalyst may be initially charged with the water-in-oil emulsion or may be fed to the reactor with or separately from components (a) and (b). When an inert organic solvent or a mixture thereof is used in combination in the production of polyacetal, polyacetal production and water removal from the system are preferably carried out simultaneously. Water is then removed azeotropically from the reaction mixture. Polyacetal is obtained in finely divided form. It is natural to take care of the mixing of the components during the reaction, for example stirring the reaction mixture. If an inert organic solvent in which polyacetal is insoluble is used, polyacetal will precipitate in the form of fine particles. In that case, it is preferable to use the emulsifiers and optionally wetting agents mentioned above. A water-soluble polyacetal is obtained. The viscosity of a 40% aqueous solution is, for example, 5 to 1000 mPa5 at 25°C, and in some cases 1000 mPa5.
The above is, for example, 1800 mPa5. Pure polyacetal does not exhibit a constant melting point below 600°C. The IR spectrum of polyacetal carboxylic acid is usually 3
430CrrI'' (breit), 293Q cm
@, showing vibration bands at 1780 ff1-' and 1740 cm-', between 1200 and 1000 crn'' and 9
It exhibits multiple absorption bands at 3 Q cm-.

The polyacetal obtained according to the invention can be used for various purposes. This polyacetal disperses pigments and also complexes heavy metal ions.

It has excellent ability to form complex compounds with ions of Kel, manganese, copper, calcium, magnesium, or chromium.

When used as an additive in detergents, this polyacetal improves the cleaning action of detergents with low or no phosphates. It also prevents graying of white textile materials, and removes residue from textile products using a phosphoric acid-free detergent containing polyacetal. Polyacetals are added, for example, to detergent compositions as enhancers in amounts of 1 to 15% by weight, based on the composition. Polyacetals are then considered as a replacement for the phosphates used hitherto.

Polyacetals are particularly superior to phosphates in that they are biodegradable. This polyacetal is a common anti-scum additive in detergent compositions (U.S. Pat. No. 3,308,066).
7 and EP 75820)). The anti-scum adhesion agent is, for example, a maleic acid polymer, a copolymer of acrylic acid and/or methacrylic acid and maleic acid, or a scum is added to the detergent composition.
It is contained in an amount of ~10% by weight. To produce detergent compositions, it is possible to start from a mixture of one or more of the above-mentioned anti-scum adhesion agents and polyacetals.

Example 1 In a flask equipped with a stirrer, a water separator and a reflux condenser, a 50% aqueous solution of glucoheptonic acid 298 F (0,6
6 mol) and 40% glyoxal aqueous solution 47.9.9
(0.33 mol) and p-dololsulfonic acid hydrate 6.6. li' and chloroform 65
Add 0g. The mixture is heated to reflux with stirring, and the water accompanying the starting materials and the water formed during the reaction are azeotropically distilled off using a water separator. 189 in 6 hours! ! of water is distilled off.

Since a precipitate is formed during the reaction, the precipitate is separated after the reaction is completed and the reaction mixture has cooled to room temperature.

When this precipitate was dried under vacuum at 25°C, a solid product of 15
1 g was obtained, which contains 165 glucoheptonic acid lactone.
Contains % by weight (HPLC measurement).

Example 2 In a flask equipped with a stirrer and a water separator, Drol 6
204 g of 50% glucoheptonic acid aqueous solution in 90 g (
0.45 mol), 6.11 g of p-+-luolsulfonic acid hydrate and 11.7 g of a 65% aqueous sodium palmitinsulfonate solution, and the mixture was heated to boiling to remove water. Remove by boiling. If boiling starts, 4
65.3 & (0.45 mol) of a 0% aqueous glyoxal solution are added over 1 hour and the water is further azeotropically distilled off.

The reaction was completed after 6 hours, and the amount of water separated was 16 in total.
5! ! It is. The reaction mixture is cooled and the polyacetal is dried separately. 1259 solid products are obtained and no glucoheptonic acid lactone is detected.

Example 3 The apparatus of Example 1 was charged with 196.1 g (0.5 mol) of a 50% aqueous solution of gluconic acid in 350 g of doluol and 72.5 g of a 40% aqueous glyoxal solution. ! i+ (0.5 mol),
Sodium sulfate salt of addition product of 25 moles of ethylene glycol to 1 mole of inoctylphenol 15
g (40% in water) and 6.41 g of p-)luolsulfonic acid hydrate are charged and 167 g of water are removed from the system in 7 hours. Removal of the doluol gives a yellow oily viscous residue that solidifies upon vacuum drying (110, p.
). The content of gluconic acid lactone is 4.9% by weight.

Example 4 The procedure is as in Example 6, except that the glyoxal solution is added dropwise to the mixture over a period of 4 hours, and at the same time the water used as solvent and the water produced by the reaction are distilled off azeotropically. After 2.5 hours of glyoxal solution addition, the total distillation of water was 1
It is 67g. 101 g of solid product are obtained, in which no gluconate lactone is detected.

39 g of the sodium sulfate salt of the addition product of 25 moles of ethylene oxide to 1 mole of phenol (40 g in water
%). The amount of water distilled out is 172 g. 115 g of solid matter remained, with a gluconate lactone content of 3
．． It is 9% by weight.

Example 6 In a flask equipped with a stirrer and a water separator, Drolol 6
90g, sodium palmitin sulfonate 11.6. !
i+ (40% in water), p-dololsulfonic acid-hydrate 6.4y and 50.9% gluco/acid aqueous solution 192.7
g (0.5 mol).

Heat the mixture to a boil while stirring vigorously. Immediately after the start of boiling, 200 g (0.5 mol) of a 25% aqueous glutardialdehyde solution was added dropwise over a period of 1 hour. By 4 hours after the start of reflux, water 278,! i' is azeotropically distilled off. The reaction mixture is then cooled to room temperature, the precipitate is filtered off with suction and dried under vacuum at 25°C. 1261 polyacetals are obtained, in which no gluconate lactones are detected.

Example 7 The procedure is as in Example 6, but instead of gluconic acid 226.9% (0.5 mol) of a 50% aqueous glucoheptonic acid solution is used. 296 g of water are distilled off within 6 hours. After cooling, filtration and drying, 161 g of solid product are obtained, the gluconate lactone content being 1% by weight.

Example 8 To the apparatus of Example 1, 690 g of doluol and 68.7 g of a 40% aqueous sodium valmitine sulfonate solution were added. ! ;1, p
-dololsulfonic acid-hydrate 6°4.9,50.9
% gluconic acid aqueous solution 192.7g (.

0.5 mol) and 94% terephthaldialdehyde 71,
5.9 (0.5 mol) and the mixture is heated to boiling with vigorous stirring. Water 145 within 5 hours after boiling starts
g is azeotropically distilled off. The reaction mixture was cooled, the precipitate was filtered with suction and dried, yielding 1521 polyacetals! obtained, in which no dialdehyde and gluconic acid are detected.

Example 9 In the apparatus of Example 1, 196 g of 50% gluconic acid aqueous solution
(0.5 mol), 40% glyoxal aqueous solution 72.6
1 (0.5 mol), 9.8 g of p-dololsulfonic acid hydrate, and 670 g of chloroform are mixed, and the mixture is heated to boiling for 8 hours with vigorous stirring. Meanwhile, 1 water
55 g are azeotropically separated. The reaction mixture is then cooled,
Decant off the chloroform. Vacuum drying of the residue at 25°C yields the polyacetal 1159, in which no gluconic acid is detected.

Example 10 In the apparatus of Example 1, 50% gluconic acid aqueous solution 255.
A mixture of 2 F (0.6 mol), 43.5 fl (0.3 mol) of 40% glyoxal aqueous solution, 5.0 g of p-dolol sulfonic acid hydrate, and 690 g of doluol was heated to boiling with stirring. do. water 15 in 4 hours
．． 19 is azeotropically distilled off.

The reaction mixture is then cooled, filtered and dried in vacuo, yielding 121 fI of polyacetal, whose gluconate lactone content is 4.2% by weight.

Example 11 Equipped with two dropping funnels, a stirrer and a water separator, a solution of doluolsulfonic acid hydrate S, CI, 9 was heated to boiling point, and a 5D% gluconic acid aqueous solution 233,2! ! (
0.6 mol) and at the same time 40% glyoxal aqueous solution 4
3.5 fi (0.3 mol) is added dropwise over 1.5 hours. 154 g of water have been distilled off azeotropically by 6.5 hours after the end of the addition. The reaction mixture is then cooled to room temperature and the precipitate is dried under suction. 115 g of solid product were obtained,
Its gluconic acid lactone content is 3.5%.

Example 12 Proceed as in Example 9, but omitting the addition of chloroform. The water used as solvent and the water formed during the reaction is removed at 400 mbar and 100°C. 125 g of polyacetal are thus obtained, the gluconic acid content of which is 8.6%. To remove the catalyst from this polyacetal, the product was dispersed in methanol, filtered, and dried under vacuum at 25°C, resulting in a polyacetal of 1
12g obtained.

Application example A, measurement of iron complex compound forming ability and iron hydroxide dispersion ability: Yes. Therefore, the test substance is mixed with iron chloride ([
11 solution until turbidity occurs.

Titration is performed automatically using a titration processor. The light transmission of the solution is then monitored using a light-induced photometer. Manual titration is not preferred. This is because the solutions often become strongly colored during the titration, which makes it difficult to see the formation of turbidity.

The degree of discoloration (due to colloidally dispersed iron hydroxide) is an indication of the tendency of the complex formed to dissociate. The rough measure is the slope of the titration curve before the equivalence point is reached. This is determined by the % permeability in 1rrLl of FeC15 solution. The reciprocal value thus obtained indicates the concentration of the complex compound.

The equivalence point is recognized as the breaking point of the titration curve.

A complex compound forming substance having a dispersion effect shows two break points,
That second point is usually not noticeable.

Pure dispersants exhibit one less distinct breakpoint. For this material, the maximum capacity (o,
Even with the addition of osmolar FeCl3 solution 5Q+++J), the equivalence point is not reached and no titration curve is obtained that can be evaluated. Substances with this property are called dispersants in the table.

Dissolve 1 mmol of the test substance in 100 ml of distilled water,
The pH is brought to 10 with -NaOH and kept constant during the titration. 0.05 m F at room temperature or 60°C
Titrate Q with eC1B solution at a rate of 4 rrtl/min. Complex compound forming ability or dispersion ability is shown by the following formula.

or 1) ws = active substance The test results are shown below.

B. Stabilization test of sodium perborate in washing liquid Hydrogen peroxide, which causes the bleaching effect of detergents containing sodium perborate, contains heavy metal ions (Fe, Cu, etc.).

catalytically cracked by Mn). Complexation of heavy metal ions prevents this. The peroxide stabilizing effect of a complex compound former is tested using the residual peroxide content after heating a heavy metal-containing washing solution. The hydrogen peroxide content is determined using potassium permanganate in acidic solution before and after standing. Two detergent compositions are utilized for testing.

(A) Phosphate-containing composition (composition is weight%) 19.3%C
32-alkylbenzole sulfonic acid Na 15.4% Sodium perborate 60.8% Sodium triphosphate 2.6% Acrylic acid/maleic acid copolymer (molecular weight 31
．． 0% Sodium sulfate 0.9% Polyacetal (B) Phosphate reduced composition (composition is weight %) 15.
0% C', 2-furkylbenzole sulfonic acid Na5.
Addition product of 11 moles of ethylene oxide to 1 mole of 0% tallow alcohol 20.0% Sodium perborate 6.0% Sodium metasilicate 1.25% Magnesium silicate 20.0% Sodium triphosphate! The 11.75% sodium sulfate 1.0% polyacetal compositions (A) and (B) were each dissolved in water having a hardness of 25° dH to prepare a washing bath. (in the washing bath (A)
The concentration of A) is 6.5 ji/A and the pH is 8.15, and the concentration of (B) in the washing bath (B) is 8 g/2 and the pH is 10.
．． It is 1. In order to investigate the stabilizing effect of perborate, 2 ppm of Fe ions and 2 ppm of C were added to washing baths (A) and (B), respectively.
u ion yO, 25pp and Mn ion 0.25p11m
in the form of an aqueous solution and leave the wash bath (A) at 80° C. for 2 hours and the wash bath (B3 at 60° C. for 2 hours).

Test of scum formation inhibition effect by C0 turbidity measurement: When a washing bath is left to stand when hot, turbidity occurs due to precipitation of sparingly soluble detergent components. The turbidity after 2 hours is a measure of the anti-settling action of the anti-scum forming agent.

For the test, a standard phosphate-free wash bath of the following composition containing 6.5 i/3 of detergent is used.

2.7% C82-alkylpenzole sulfonic acid Na3
．． 25 ethylene oxide to 1 mole of 3% tallow alcohol
Mol addition products 10.8% Sodium metasilicate 27.0% Sodium carbonate 2.1% CMC 1.8% Acrylic acid/maleic acid copolymer C Molecular weight 70
C100) 92% polyacetal 46.1% sodium sulfate standard wash bath is heated for at least 2 hours in water at 22.4° dH, and then the turbidity is measured by a pyrometer [low turbidity (in NTU)] The value means better activity of the detergent, higher value means poorer activity].

D. Measurement of calcium binding ability: Dissolve 1 g of active substance in 10 ml of 10% sodium carbonate solution,
The pH is brought to 11 using IN-NaOH.

Titrate with 0.35 m calcium acetate solution, keeping the pH value constant, until turbidity begins.

Claims (1)

[Claims] 1. The following formula OHC-A_n-CHO (A is -CH_2-, -CH_2-CH_2-, -CH
_2-CH_2-CH_2-, -CH_2-CH_2-
CH_2-CH_2-, means ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
dialdehyde (a) (n is 0 or 1)
a polyol carboxylic acid (b) having 5 to 7 carbon atoms and at least 3 OH groups; (a):(b)
A polyacetal obtained by reacting in an aqueous medium in the presence of an acidic catalyst in a molar ratio of 1:0.25 to 4. 2. The following formula OHC-A_n-CHO (A is -CH_2-, -CH_2-CH_2-, -CH
_2-CH_2-CH_2-, -CH_2-CH_2-
CH_2-CH_2-, means ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
dialdehyde (a) (n is 0 or 1)
a polyol carboxylic acid (b) having 5 to 7 carbon atoms and at least 3 OH groups; (a):(b)
A process for producing polyacetals, characterized in that the reaction is carried out in an aqueous medium in the presence of an acidic catalyst at a temperature below 140°C in a molar ratio of 1:0.25 to 4, and water is removed from the reaction mixture. 3. Process according to claim 2, characterized in that both components are reacted in a molar ratio of 1:0.5-2 at a temperature of 60-110<0>C. 4. Process according to claim 2 or 3, characterized in that glyoxal, glutardialdehyde, terephthalic dialdehyde or a mixture thereof is used as the dialdehyde. 5. The method according to claim 2 or 3, characterized in that gluconic acid and/or glucoheptonic acid is used as the polyol carboxylic acid. 6. The method according to any one of claims 2 to 5, characterized in that the reaction is carried out in an inert organic solvent in which the polyacetal is insoluble. 7. Process according to claim 6, characterized in that the reaction is carried out in the presence of an additional water-in-oil emulsifier. 8. A method of using the polyacetal according to claim 1 as a detergent. 9. A method of using the polyacetal according to claim 1 as a complex compound former.